Infrared Photodissociation Spectroscopy of Mass-Selected Heteronuclear Iron–Copper Carbonyl Cluster Anions in the Gas Phase

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2015-05, Vol.119 (18), p.4142-4150
• Main Authors: Zhang, Ning, Luo, Mingbiao, Chi, Chaoxian, Wang, Guanjun, Cui, Jieming, Zhou, Mingfei
• Format: Article
• Language: English
• Subjects: Anions; Bonding; Carbonyls; Clusters; Gas phases; Infrared; Photodissociation; Spectroscopy
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.5b02442

Mass-selected heteronuclear iron–copper carbonyl cluster anions CuFe­(CO) n – (n = 4–7) are studied by infrared photodissociation spectroscopy in the carbonyl stretching frequency region in the gas phase. The cluster anions are produced via a laser vaporization supersonic cluster ion source. Their geometric structures are determined by comparison of the experimental spectra with those calculated by density functional theory. The experimentally observed CuFe­(CO) n – (n = 4–7) cluster anions are characterized to have (OC)4Fe–Cu­(CO) n−4 structures, each involving a C 3v symmetry Fe­(CO)4 – building block. Bonding analysis indicates that the Fe–Cu bond in the CuFe­(CO) n – (n = 4–7) cluster anions is a σ type single bond with the iron center possessing the most favored 18-electron configuration. The results provide important new insight into the structure and bonding of hetronuclear transition metal carbonyl cluster anions.